Curable polysilsesquioxane compound, production method thereof, curable composition, cured product and use method of curable composition

ABSTRACT

The present invention is a curable polysilsesquioxane compound comprising at least one structural unit represented by CHR 1 X 0 -D-SiO 3/2 ,
         the curable polysilsesquioxane compound having a  29 Si nuclear magnetic resonance spectrum that has a first peak top within a range of −73 ppm or more and less than −65 ppm, has a second peak top within a range of −82 ppm or more and less than −73 ppm, and substantially does not have a peak within a range of −65 ppm or more and less than −55 ppm, and   a method for producing the curable polysilsesquioxane compound, and   a curable composition comprising the curable polysilsesquioxane compound and a silane coupling agent, and   a cured product obtained by heating the curable composition, and   a method for using the curable polysilsesquioxane compound or the curable composition, as an optical device-securing material.

TECHNICAL FIELD

The present invention relates to a curable polysilsesquioxane compound that produces a cured product that exhibits high adhesion, excellent heat resistance, and excellent delamination resistance, and rarely produces cracks, a method for producing the same, a curable composition, a cured product obtained by curing the curable composition, and a method for using the curable polysilsesquioxane compound or the curable composition as an optical device-securing material.

BACKGROUND ART

A light-emitting device (e.g., laser (e.g., semiconductor laser diode (LD)) and light-emitting diode (LED)), a light-receiving device, a hybrid optical device, an optical integrated circuit, and the like are known as an optical device. In recent years, an optical device that emits blue light or white light (i.e., an optical device having a shorter emission peak wavelength) has been developed, and widely used. There is a tendency that the brightness of a light-emitting device having a short emission peak wavelength is significantly increased, and the amount of heat generated by such an optical device further increases.

A curable composition (optical device-securing material composition) is used as an adhesive and a sealing material for such an optical device.

Along with a recent increase in brightness of an optical device, however, a cured product of the optical device-securing composition may deteriorate due to long-term exposure to high-energy light or high-temperature heat generated by the optical device, whereby delamination or cracks may occur, for example.

In order to solve this problem, Patent Literature 1 to 3 propose an optical device-securing material composition that includes a polysilsesquioxane compound as the main component.

A polysilsesquioxane compound is a compound represented by (R⁰SiO_(3/2))_(n)(wherein R⁰ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or the like), and has intermediate properties between inorganic silica (SiO₂) and an organic silicone ((R⁰ ₂SiO)_(n)).

However, the optical device-securing compositions disclosed in Patent Literature 1 to 3 that include a polysilsesquioxane compound as the main component may not produce a cured product that exhibits sufficient heat resistance and delamination resistance while maintaining sufficient adhesion.

Therefore, development of a curable composition that can produce a cured product that exhibits high adhesion, excellent heat resistance, and excellent delamination resistance, and rarely produces cracks has been desired.

Patent Literature 4 discloses a semiconductor light-emitting device member that has a solid Si-nuclear magnetic resonance spectrum that has at least one peak selected from the group consisting of a peak whose peak top position is within the chemical shift range of −40 ppm or more and 0 ppm or less, and whose full width at half maximum is within a specific range, and a peak whose peak top position is within the chemical shift range of −80 ppm or more and less than −40 ppm, and whose full width at half maximum is within a specific range, has a silicon content of 20 wt % or more, and has a silanol content of 0.1 to 10 wt %.

CITATION LIST Patent Literature

Patent Literature 1: JP-A-2004-359933

Patent Literature 2: JP-A-2005-263869

Patent Literature 3: JP-A-2006-328231

Patent Literature 4: JP-A-2007-112975 (US2009/0008673A1)

SUMMARY OF INVENTION Technical Problem

The invention was conceived in view of the above situation. An object of the invention is to provide a curable compound and a curable composition that can produce a cured product that exhibits high adhesion, excellent heat resistance, and excellent delamination resistance, and rarely produces cracks, a method for producing the curable compound, a cured product obtained by curing the curable composition, and a method for using the curable compound or the curable composition.

Solution to Problem

The inventors conducted extensive studies in order to solve the above technical problem. As a result, the inventors found that a curable polysilsesquioxane compound that includes at least one structural unit represented by CHR¹X⁰-D-SiO_(3/2), and has a ²⁹Si nuclear magnetic resonance spectrum that has a first peak top within the range of −73 ppm or more and less than −65 ppm, has a second peak top within the range of −82 ppm or more and less than −73 ppm, and substantially does not have a peak within the range of −65 ppm or more and less than −55 ppm, can produce a cured product that exhibits high adhesion, excellent heat resistance, and excellent delamination resistance, and rarely produces cracks. This finding has led to the completion of the invention.

Several aspects of the invention provide the following curable polysilsesquioxane compound (see (1) to (4)), method for producing a curable polysilsesquioxane compound (see (5) to (8)), curable composition (see (9)), cured product (see (10)), and method for using a curable polysilsesquioxane compound or a curable composition as an optical device-securing material (see (11)).

(1) A curable polysilsesquioxane compound including at least one structural unit represented by CHR¹X⁰-D-SiO_(3/2) (wherein R¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, X⁰ is a halogen atom, a cyano group, or a group represented by OG (wherein G is a protecting group for a hydroxyl group), and D is a single bond, or a substituted or unsubstituted divalent organic group having 1 to 20 carbon atoms),

the curable polysilsesquioxane compound having a ²⁹Si nuclear magnetic resonance spectrum that has a first peak top within the range of −73 ppm or more and less than −65 ppm, has a second peak top within the range of −82 ppm or more and less than −73 ppm, and substantially does not have a peak within the range of −65 ppm or more and less than −55 ppm.

(2) The curable polysilsesquioxane compound according to (1), further including at least one structural unit represented by R²SiO_(3/2) (wherein R² is an alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group).

(3) The curable polysilsesquioxane compound according to (1) or (2), the curable polysilsesquioxane compound having the ²⁹Si nuclear magnetic resonance spectrum in which the ratio of an integral value (P2) of a peak within the range of −82 ppm or more and less than −73 ppm to an integral value (P1) of a peak within the range of −73 ppm or more and less than −65 ppm is 60 to 90%. (4) The curable polysilsesquioxane compound according to any one of (1) to (3), the curable polysilsesquioxane compound being a compound having a mass average molecular weight of 800 to 5,000. (5) A method for producing the curable polysilsesquioxane compound according to any one of (1) to (4), the method including a step (I) that subjects at least one compound represented by the following formula (1) to polycondensation in the presence of a polycondensation catalyst, CHR¹X⁰-D-Si(OR³)₃  (1) wherein R¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, X⁰ is a halogen atom, a cyano group, or a group represented by OG (wherein G is a protecting group for a hydroxyl group), D is a single bond, or a substituted or unsubstituted divalent organic group having 1 to 20 carbon atoms, and R³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, provided that a plurality of R³ are either identical to or different from each other. (6) The method according to (5), wherein the step (I) subjects a mixture that includes at least one compound represented by the formula (1) and at least one compound represented by the following formula (2) to polycondensation in the presence of the polycondensation catalyst, R²Si(OR⁴)₃  (2) wherein R² is an alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group, and R⁴ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, provided that a plurality of R⁴ are either identical to or different from each other. (7) The method according to (5) or (6), wherein the polycondensation catalyst is at least one acid catalyst selected from the group consisting of hydrochloric acid, boric acid, citric acid, acetic acid, sulfuric acid, and methanesulfonic acid. (8) The method according to (7), further including a step (II) that adds an organic solvent to the reaction mixture obtained by the step (I) to dissolve the polycondensate to obtain a solution, adds a base to the solution in a molar equivalent equal to or larger than that of the acid catalyst, and then effects polycondensation. (9) A curable composition including the curable polysilsesquioxane compound according to any one of (1) to (4), and a silane coupling agent. (10) A cured product obtained by heating the curable composition according to (9). (11) A method for using the curable polysilsesquioxane compound according to any one of (1) to (4), or the curable composition according to (9), as an optical device-securing material.

Advantageous Effects of Invention

The curable polysilsesquioxane compound according to the invention, and the curable composition according to the invention that includes at least the curable polysilsesquioxane compound according to the invention and a silane coupling agent, can produce a cured product that exhibits high adhesion, excellent heat resistance, and excellent delamination resistance, and rarely produces cracks.

The method for producing a curable polysilsesquioxane compound according to the invention can efficiently produce the curable polysilsesquioxane compound according to the invention.

The cured product according to the invention exhibits high adhesion even when exposed to high-energy light, or subjected to a high temperature, and can sufficiently seal an optical device for a long time.

The curable polysilsesquioxane compound according to the invention and the curable composition according to the invention may be used as an optical device-securing material. In particular, the curable polysilsesquioxane compound according to the invention and the curable composition according to the invention may suitably be used as an optical device adhesive and an optical device sealing material.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is the ²⁹Si-NMR spectrum chart of the curable polysilsesquioxane compound of Example 1.

FIG. 2 is the ²⁹Si-NMR spectrum chart of the curable polysilsesquioxane compound of Comparative Example 1.

DESCRIPTION OF EMBODIMENTS

A curable polysilsesquioxane compound, a method for producing a curable polysilsesquioxane compound, a curable composition, a cured product, and a method for using the curable polysilsesquioxane compound or the curable composition as an optical device-securing material according to the exemplary embodiments of the invention are described in detail below.

1) Curable Polysilsesquioxane Compound

A curable polysilsesquioxane compound according to one embodiment of the invention includes at least one structural unit represented by CHR¹X⁰-D-SiO_(3/2), the curable polysilsesquioxane compound having a ²⁹Si nuclear magnetic resonance spectrum that has a first peak top within the range of −73 ppm or more and less than −65 ppm, has a second peak top within the range of −82 ppm or more and less than −73 ppm, and substantially does not have a peak within the range of −65 ppm or more and less than −55 ppm.

It is preferable that a curable composition according to one embodiment of the invention be a thermosetting composition.

It is preferable that the curable polysilsesquioxane compound according to one embodiment of the invention further include at least one structural unit represented by R²SiO_(3/2) in addition to the structural unit represented by CHR¹X⁰-D-SiO_(3/2).

R¹ included in CHR¹X⁰-D-SiO_(3/2) is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Examples of the alkyl group having 1 to 6 carbon atoms that may be represented by R¹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, and the like.

It is preferable that R¹ be a hydrogen atom.

X⁰ is a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, or iodine atom), a cyano group, or a group represented by OG.

G is a protecting group for a hydroxyl group. The protecting group for a hydroxyl group is not particularly limited, and may be an arbitrary protecting group that is known as a protecting group for a hydroxyl group. Examples of the protecting group include an acyl-based protecting group; a silyl-based protecting group such as a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, and a t-butyldiphenylsilyl group; an acetal-based protecting group such as a methoxymethyl group, a methoxyethoxymethyl group, a 1-ethoxyethyl group, a tetrahydropyran-2-yl group, and a tetrahydrofuran-2-yl group; an alkoxycarbonyl-based protecting group such as a t-butoxycarbonyl group; a methyl group, an ethyl group, a t-butyl group, an octyl group, an allyl group, a triphenylmethyl group, a benzyl group, a p-methoxybenzyl group, a fluorenyl group, a trityl group, and a benzhydryl group; and the like. It is preferable that G be an acyl-based protecting group.

The acyl-based protecting group is represented by —C(═O)R⁵ (wherein R⁵ is an alkyl group having 1 to 6 carbon atoms (e.g., methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, or n-pentyl group), or a substituted or unsubstituted phenyl group).

R² is an alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group. Note that the expression “substituted or unsubstituted” used herein in connection with a group or the like means that the group or the like is unsubstituted, or substituted with a substituent (hereinafter the same).

Examples of a substituent that may substitute the phenyl group (that is either substituted or unsubstituted) that may be represented by R⁵ include an alkyl group (alkyl group having 1 to 6 carbon atoms) such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group; a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom; an alkoxy group (alkoxy group having 1 to 6 carbon atoms) such as a methoxy group and an ethoxy group; and the like.

It is preferable that X⁰ be a chlorine atom or a group selected from a group represented by OG′ (wherein G′ is an acyl-type protecting group) and a cyano group, more preferably a chlorine atom or a group selected from an acetoxy group and a cyano group, and particularly preferably a cyano group, from the viewpoint of availability and a capability to produce a cured product that exhibits high adhesion.

D is a single bond, or a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms.

Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, an alkynylene group having 2 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, a divalent group having 7 to 20 carbon atoms obtained by combining an alkylene group, an alkenylene group, or an alkynylene group with an arylene group, and the like.

Examples of the alkylene group having 1 to 20 carbon atoms include a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, and the like.

Examples of the alkenylene group having 2 to 20 carbon atoms include a vinylene group, a propenylene group, a butenylene group, a pentenylene group, and the like.

Examples of the alkynylene group having 2 to 20 carbon atoms include an ethynylene group, a propynylene group, and the like.

Examples of the arylene group having 6 to 20 carbon atoms include an o-phenylene group, an m-phenylene group, a p-phenylene group, a 2,6-naphthylene group, and the like.

Examples of a substituent that may substitute the alkylene group having 1 to 20 carbon atoms, the alkenylene group having 2 to 20 carbon atoms, and the alkynylene group having 2 to 20 carbon atoms include a halogen atom such as a fluorine atom and a chlorine atom; an alkoxy group (alkoxy group having 1 to 6 carbon atoms) such as a methoxy group and an ethoxy group; an alkylthio group (alkylthio group having 1 to 6 carbon atoms) such as a methylthio group and an ethylthio group; an alkoxycarbonyl group (alkoxycarbonyl group having 2 to 8 carbon atoms) such as a methoxycarbonyl group and an ethoxycarbonyl group; and the like.

Examples of a substituent that may substitute the arylene group having 6 to 20 carbon atoms include a cyano group; a nitro group; a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom; an alkyl group (alkyl group having 1 to 6 carbon atoms) such as a methyl group and an ethyl group; an alkoxy group (alkoxy group having 1 to 6 carbon atoms) such as a methoxy group and an ethoxy group; an alkylthio group (alkylthio group having 1 to 6 carbon atoms) such as a methylthio group and an ethylthio group; and the like.

These substituents may be bonded to the alkylene group, the alkenylene group, the alkynylene group, and the arylene group at an arbitrary position. A plurality of identical or different substituents may be bonded to the alkylene group, the alkenylene group, the alkynylene group, and the arylene group.

Examples of the divalent group obtained by combining a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted alkynylene group with a substituted or unsubstituted arylene group, include a group in which at least one group among a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, and a substituted or unsubstituted alkynylene group is bonded linearly (in series) to at least one substituted or unsubstituted arylene group, and the like. Specific examples of the divalent group include the groups respectively represented by the following formulas, and the like.

It is preferable that D be an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and particularly preferably a methylene group or an ethylene group, since a cured product that exhibits high adhesion can be obtained.

R² included in R²SiO_(3/2) is an alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

Examples of the alkyl group having 1 to 20 carbon atoms that may be represented by R² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an isobutyl group, an s-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group, an n-decyl group, an n-dodecyl group, and the like.

Examples of the aryl group (that is either substituted or unsubstituted) include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an anthracenyl group, and the like.

Examples of a substituent that may substitute the aryl group include an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group, and a t-butyl group; an alkoxy group having 1 to 6 carbon atoms, such as a methoxy group, an ethoxy group, and an isopropoxy group; a halogen atom such as a fluorine atom and a chlorine atom; and the like.

A polysilsesquioxane compound is a silicon-based polymer that is obtained by subjecting a trifunctional organosilane compound to polycondensation, and exhibits inorganic properties due to the siloxane (Si—O—Si) bond included in the main chain, and organic properties due to the organic group included in the side chain.

The structure of the curable polysilsesquioxane compound according to one embodiment of the invention is not particularly limited. Examples of the structure of the curable polysilsesquioxane compound according to one embodiment of the invention include a ladder structure, a double decker structure, a basket structure, a partially cleaved basket structure, a cyclic structure, and a random structure.

The curable polysilsesquioxane compound according to one embodiment of the invention is a polymer that includes at least one structural unit represented by RSiO_(3/2) (wherein R is the group represented by CHR¹X⁰-D-, or R² (hereinafter the same)).

When the curable polysilsesquioxane compound according to one embodiment of the invention is a copolymer that includes two or more structural units represented by CHR¹X⁰-D-SiO_(3/2), or includes the structural unit represented by CHR¹X⁰-D-SiO_(3/2) and the structural unit represented by R²SiO_(3/2), the curable polysilsesquioxane compound according to one embodiment of the invention may be a random copolymer or a block copolymer, but is preferably a random copolymer from the viewpoint of availability and the like.

The structural unit represented by RSiO_(3/2) included in the curable polysilsesquioxane compound according to one embodiment of the invention is normally referred to as “T-site”, and has a structure in which three oxygen atoms and one group (R) are bonded to the silicon atom.

Specific examples of the structure of the T-site include structures respectively represented by the following formulas (a) to (c).

Note that R⁰ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms that may be represented by R⁰ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an isobutyl group, an s-butyl group, an n-pentyl group, an n-hexyl group, and the like. Note that a plurality of R⁰ are either identical to or different from each other. The symbol “*” in the formulas (a) to (c) represents that an Si atom is bonded.

The curable polysilsesquioxane compound according to one embodiment of the invention is normally soluble in various organic solvents including a halogen-based solvent such as chloroform, a ketone-based solvent such as acetone, an aromatic hydrocarbon-based solvent such as benzene, a sulfur-containing solvent such as dimethyl sulfoxide, an ether-based solvent such as tetrahydrofuran, an ester-based solvent such as ethyl acetate, a mixed solvent including two or more solvents among these solvents, and the like. It is preferable that the curable polysilsesquioxane compound according to one embodiment of the invention have a solubility in chloroform at 20° C. of 1 mg/100 ml or more, more preferably 20 mg/100 ml or more, and particularly preferably 40 mg/100 ml or more.

Since the curable polysilsesquioxane compound according to one embodiment of the invention is normally soluble in various organic solvents, the curable polysilsesquioxane compound can be subjected to ²⁹Si-NMR measurement in a solution state (dissolved state).

When the curable polysilsesquioxane compound according to one embodiment of the invention is subjected to ²⁹Si-NMR measurement, four peaks T0 to T3 attributed to the T-site are normally observed at −85 to −55 ppm.

It is considered that the peak T0 is attributed to a silicon atom that does not form a siloxane bond, the peak T1 is attributed to a silicon atom that forms one siloxane bond (i.e., the silicon atom included in the structure represented by the formula (c)), the peak T2 is attributed to a silicon atom that forms two siloxane bonds (i.e., the silicon atom included in the structure represented by the formula (b)), and the peak T3 is attributed to a silicon atom that forms three siloxane bonds (i.e., the silicon atom included in the structure represented by the formula (a)).

The curable polysilsesquioxane compound according to one embodiment of the invention has a ²⁹Si nuclear magnetic resonance spectrum that has the first peak top (corresponding to the peak T2) within the range of −73 ppm or more and less than −65 ppm, has the second peak top (corresponding to the peak T3) within the range of −82 ppm or more and less than −73 ppm, and substantially does not have a peak (corresponding to the peak T1) within the range of −65 ppm or more and less than −55 ppm.

The expression “substantially does not have a peak (corresponding to the peak T1) within the range of −65 ppm or more and less than −55 ppm” means that, when the curable polysilsesquioxane compound according to one embodiment of the invention is subjected to ²⁹Si-NMR measurement, a peak (corresponding to the peak T1) is not observed within the range of −65 ppm or more and less than −55 ppm, or, even when a peak (corresponding to the peak T1) is observed within the range of −65 ppm or more and less than −55 ppm, the ratio of the integral value of the peak (corresponding to the peak T1) within the range of −65 ppm or more and less than −55 ppm to the integral value of the peak (corresponding to the peak T2) within the range of −73 ppm or more and less than −65 ppm is less than 0.5%.

It is preferable that the ratio of the integral value (P2) of the peak (corresponding to the peak T3) within the range of −82 ppm or more and less than −73 ppm to the integral value (P1) of the peak (corresponding to the peak T2) within the range of −73 ppm or more and less than −65 ppm be 60 to 90%, since the advantageous effects of the invention are further improved.

It is conjectured that the curable polysilsesquioxane compound can produce a cured product that exhibits high adhesion even at a high temperature, exhibits excellent heat resistance and excellent delamination resistance, and rarely produces cracks for the following reasons when the curable polysilsesquioxane compound has a ²⁹Si-NMR spectrum that substantially does not have a peak top within the range of −65 ppm or more and less than −55 ppm, has the first peak top within the range of −73 ppm or more and less than −65 ppm, and has the second peak top within the range of −82 ppm or more and less than −73 ppm.

Specifically, when the curable polysilsesquioxane compound has a ²⁹Si-NMR spectrum that has the peak T1, the curable polysilsesquioxane compound has a structure in which a number of components are eliminated due to dehydration or dealcoholization condensation when the curable polysilsesquioxane compound is cured by heating, and voids easily occur due to the eliminated components, whereby a decrease in adhesion occurs. On the other hand, when the curable polysilsesquioxane compound has a ²⁹Si-NMR spectrum that has the peak T3 in a high ratio, it is considered that the curable polysilsesquioxane compound produces a cured product that has a relatively dense structure, and exhibits sufficient adhesion.

The ²⁹Si-NMR spectrum may be measured as described below, for example.

Sample Conditions

Deuterated chloroform is used as a measurement solvent, and Fe(acac)₃ is used as a relaxation reagent in order to reduce the relaxation time.

The intensity of each peak is normalized using the area of tetramethylsilane (internal standard) (=1) to remove the effects of an error during each measurement.

Device Conditions

An NMR measurement device (e.g., “AV-500” manufactured by Bruker BioSpin K.K.) is used.

²⁹Si resonant frequency: 99.352 MHz

Probe: 5 mm (diameter) solution probe

Measurement temperature: 25° C.

Sample rotational speed: 20 kHz

Measurement method: inverse gated decoupling method

²⁹Si flip angle: 90°

²⁹Si 90° pulse width: 8.0 μs

Repetition time: 5 s

Integration count: 9,200

Observation width: 30 kHz

Waveform Analysis

The chemical shift of each peak of the spectrum subjected to a Fourier transform is calculated from the position of the peak top, and integrated.

The mass average molecular weight (Mw) of the curable polysilsesquioxane compound according to one embodiment of the invention is preferably 800 to 5,000, and more preferably 1,000 to 3,000.

The mass average molecular weight (Mw) of the curable polysilsesquioxane compound may be determined as a standard polystyrene-equivalent value by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, for example.

The molecular weight distribution (Mw/Mn, hereinafter referred to as “PDI”) of the curable polysilsesquioxane compound according to one embodiment of the invention is not particularly limited, but is normally 1.0 to 6.0, and preferably 1.0 to 3.0. When the molecular weight distribution is within the above range, a cured product that exhibits improved adhesion can be obtained.

The curable polysilsesquioxane compound according to one embodiment of the invention may be produced using an arbitrary method. Note that it is preferable to produce the curable polysilsesquioxane compound according to one embodiment of the invention using a method for producing a curable polysilsesquioxane compound according to one embodiment of the invention (described below).

2) Method for Producing Curable Polysilsesquioxane Compound

The method for producing a curable polysilsesquioxane compound according to one embodiment of the invention includes a step (I) that subjects at least one compound represented by the following formula (1) to polycondensation in the presence of a polycondensation catalyst. CHR¹X⁰-D-Si(OR³)₃  (1)

wherein R¹, X⁰, and D are the same as defined above, and R³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (as defined above in connection with R⁰), provided that a plurality of R³ are either identical to or different from each other.

It is preferable that the method for producing a curable polysilsesquioxane compound according to one embodiment of the invention include the step (I) that subjects at least one compound represented by the formula (1) and at least one compound represented by the following formula (2) to polycondensation in the presence of the polycondensation catalyst. R²Si(OR⁴)₃  (2)

wherein R² is the same as defined above, and R⁴ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (as defined above in connection with R⁰), provided that a plurality of R⁴ are either identical to or different from each other.

Step (I)

In the step (I), the silane compound represented by the formula (1) (hereinafter may be referred to as “silane compound (1)”) is subjected to polycondensation in the presence of the polycondensation catalyst, or the silane compound (1) and the silane compound represented by the formula (2) (hereinafter may be referred to as “silane compound (2)”) are subjected to polycondensation in the presence of the polycondensation catalyst.

Specific examples of the silane compound (1) include cyanomethyltrimethoxysilane, cyanomethyltriethoxysilane, 1-cyanoethyltrimethoxysilane, 2-cyanoethyltrimethoxysilane, 2-cyanoethyltriethoxysilane, 2-cyanoethyltripropoxysilane, 3-cyanopropyltrimethoxysilane, 3-cyanopropyltriethoxysilane, 3-cyanopropyltripropoxysilane, 3-cyanopropyltributoxysilane, 4-cyanobutyltrimethoxysilane, 5-cyanopentyltrimethoxysilane, 2-cyanopropyltrimethoxysilane, 2-(cyanomethoxy)ethyltrimethoxysilane, 2-(2-cyanoethoxy)ethyltrimethoxysilane, o-(cyanomethyl)phenyltripropoxysilane, m-(cyanomethyl)phenyltrimethoxysilane, p-(cyanomethyl)phenyltriethoxysilane, p-(2-cyanoethyl)phenyltrimethoxysilane, 2-chloroethyltriethoxysilane, 2-bromoethyltriethoxysilane, methoxymethyltriethoxysilane, methylthiomethyltriethoxysilane, methoxycarbonylmethyltriethoxysilane, 2-acryloyloxyethyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, and the like.

It is preferable that the silane compound (1) be a compound that includes a 2-cyanoethyl group or a compound that includes a 3-cyanopropyl group, since a cured product that exhibits higher adhesion can be obtained.

Specific examples of the silane compound (2) include alkyltrialkoxysilane compounds such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-butyltriethoxysilane, isobutyltrimethoxysilane, n-pentyltriethoxysilane, n-hexyltrimethoxysilane, isooctyltriethoxysilane, dodecyltrimethoxysilane, methyldimethoxyethoxysilane, and methyldiethoxymethoxysilane;

a substituted or unsubstituted phenyltrialkoxysilane compounds such as phenyltrimethoxysilane, 4-methoxyphenyltrimethoxysilane, 2-chlorophenyltrimethoxysilane, phenyltriethoxysilane, 2-methoxyphenyltriethoxysilane, phenyldimethoxyethoxysilane, and phenyldiethoxymethoxysilane; and the like.

These silane compounds may be used either alone or in combination. It is preferable to use two or more silane compounds from the viewpoint of adjusting adhesion, heat resistance, and discoloration resistance.

The polycondensation catalyst is not particularly limited. Note that it is preferable to use an acid catalyst since the curable polysilsesquioxane compound according to one embodiment of the invention can be easily obtained. Examples of the acid catalyst include an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and boric acid; an organic acid such as methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, acetic acid, trifluoroacetic acid, and citric acid; and the like.

It is preferable to use at least one acid catalyst selected from hydrochloric acid, boric acid, citric acid, acetic acid, sulfuric acid, and methanesulfonic acid, and particularly preferably hydrochloric acid, since the target product can be easily obtained.

The polycondensation catalyst is used in an appropriate amount (ratio) taking account of the type of the silane compound (1), the type of the polycondensation catalyst, and the like. The polycondensation catalyst is normally used in a ratio of 0.05 to 30 mol %, preferably 0.1 to 10 mol %, and more preferably 0.2 to 5 mol %, based on the total number of moles of the silane compound (1).

A solvent may be appropriately selected taking account of the type and the amount of the silane compound (1), the type and the amount of the polycondensation catalyst, and the like. Examples of the solvent include water; aromatic hydrocarbons such as benzene, toluene, and xylene; esters such as methyl acetate, ethyl acetate, propyl acetate, and methyl propionate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, s-butyl alcohol, and t-butyl alcohol; and the like. These solvents may be used either alone or in combination.

It is preferable to use water or alcohols, and more preferably water, since the target product can be easily obtained.

The solvent is normally used in an amount of 1 to 1,000 ml, preferably 10 to 500 ml, and more preferably 50 to 200 ml, based on 1 mol of the silane compound (1).

The reaction temperature and the reaction time employed when subjecting the silane compound (1) to polycondensation (reaction) are appropriately selected taking account of the type and the amount of the silane compound (1), the type and the amount of the polycondensation catalyst, the type and the amount of the solvent, and the like.

The reaction temperature is normally within the range from 0° C. to the boiling point of the solvent, and preferably within the range from 20 to 100° C. If the reaction temperature is too low, condensation may not proceed sufficiently. If the reaction temperature is too high, it may be difficult to suppress gelation.

The reaction time is normally within the range from several minutes to 10 hours.

It is preferable to effect the reaction at a reaction temperature of 5 to 35° C. for several minutes to several hours, and then effect the reaction at a reaction temperature of 35 to 100° C. for several tens of minutes to several hours.

It is preferable that the method for producing a curable polysilsesquioxane compound according to one embodiment of the invention further include a step (II) described below when the step (I) (polymerization reaction) is effected in the presence of the acid catalyst.

It is possible to easily obtain the curable polysilsesquioxane compound according to one embodiment of the invention that has the desired ²⁹Si-NMR spectrum pattern by providing the step (II) that adds an organic solvent to the reaction mixture obtained by the step (I) that uses the acid catalyst to dissolve the polycondensate, and then effects polycondensation (as described below).

Step (II)

In the step (II), an organic solvent is added to the reaction mixture obtained by the step (I) to dissolve the polycondensate to obtain a solution, a base is added to the solution in a molar equivalent equal to or larger than that of the acid catalyst, and polycondensation is then effected.

The organic solvent used in the step (II) is not particularly limited as long as the organic solvent can dissolve the polycondensate produced by the step (I). It is preferable to use a water-immiscible organic solvent having a boiling point of about 60° C. to about 100° C. from the viewpoint of ease of post-treatment. The term “water-immiscible organic solvent” used herein refers to an organic solvent that has a solubility in water at 25° C. of 10 g/L or less, and is normally separated from water.

Examples of such an organic solvent include aromatic compounds such as benzene; esters such as ethyl acetate and propyl acetate; ketones such as methyl isobutyl ketone; aliphatic hydrocarbons such as heptane and cyclohexane; halogenated hydrocarbons such as chloroform; an ethers such as tetrahydrofuran; and the like.

The organic solvent may be used in an arbitrary amount (ratio) as long as the polycondensate can be dissolved in the organic solvent. The organic solvent is normally used in a ratio of 0.5 to 5 parts by mass, and preferably 1 to 3 parts by mass, based on 1 part by mass of the silane compound (1).

It is preferable to use ammonia or an organic base (e.g., pyridine and triethylamine) as the base since the target product can be easily obtained. It is more preferable to use ammonia as the base from the viewpoint of ease of handling.

The base is normally used in a ratio of 1.2 to 5 equivalents, and preferably 1.5 to 2.5 equivalents, based on the acid catalyst used in the step (I).

After the addition of the base, polycondensation is normally effected at 50 to 100° C. for 30 minutes to 10 hours. Note that the reaction time may be adjusted depending on the reaction scale and the like.

It is possible to obtain the curable polysilsesquioxane compound according to one embodiment of the invention that has a high molecular weight and substantially does not have a peak within the range of −65 ppm or more and less than −55 ppm, by effecting polycondensation in the step (II) in addition to polycondensation that is effected in the step (I).

After completion of the reaction, a post-treatment operation that is normally employed when implementing organic synthesis is performed. For example, the reaction mixture is washed with purified water, and the organic layer is concentrated and dried to obtain the target curable polysilsesquioxane compound.

A curable polysilsesquioxane compound having the desired ²⁹Si-NMR spectrum pattern can be obtained by appropriately setting the reaction conditions as described above taking account of the type of the silane compound (1), the type of the catalyst, and the like.

It is considered that the curable polysilsesquioxane compound according to one embodiment of the invention is represented by the following formula (a-1) when the curable polysilsesquioxane compound is produced using the silane compound (1) and the silane compound (2). (CHR¹X⁰-D-SiO_(3/2))_(m)(R²SiO_(3/2))_(n)(CHR¹X⁰-D-SiZ¹O_(2/2))_(o)(R²SiZ⁰O_(2/2))_(p)(CHR¹X⁰-D-SiZ¹ ₂O_(1/2))_(q)(R²SiZ²O_(1/2))_(r)   (a-1) wherein R¹, R², X⁰, and D are the same as defined above, Z¹ is a group represented by —OR³ (wherein R³ is the same as defined above), Z² is a group represented by —OR⁴ (wherein R⁴ is the same as defined above), q and r are substantially 0, and m to p are independently a positive integer. 3) Curable Composition

The curable composition according to one embodiment of the invention includes the curable polysilsesquioxane compound according to one embodiment of the invention, and a silane coupling agent. It is preferable that the curable composition according to one embodiment of the invention include the curable polysilsesquioxane compound according to one embodiment of the invention in a ratio of 60 to 99.7 mass %, more preferably 70 to 95 mass %, and still more preferably 80 to 90 mass %. When the curable composition includes the curable polysilsesquioxane compound according to one embodiment of the invention in a ratio within the above range, and also includes the silane coupling agent, the curable composition can produce a cured product that exhibits high adhesion, excellent heat resistance, and excellent delamination resistance, and rarely produces cracks.

The silane coupling agent is not particularly limited. Examples of the silane coupling agent include a silane compound that includes a vinyl group, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, p-styryltrimethoxysilane, and vinyltriacetoxysilane; a silane compound that includes a halogen atom, such as γ-chloropropyltrimethoxysilane, chloromethyltrimethoxysilane, and chloromethylphenethyltrimethoxysilane; a silane compound that includes a (meth)acryloxy group, such as γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, and 3-acryloxyprophyltrimethoxysilane; a silane compound that includes a mercapto group, such as γ-mercaptopropyltrimethoxysilane; a silane compound that includes a ureido group, such as 3-ureidopropyltriethoxysilane; a silane compound that includes an isocyanate group, such as 3-isocyanatopropyltriethoxysilane; a silane compound that includes an isocyanurate group, such as 1,3,5-N-tris(3-trimethoxysilylpropyl) isocyanurate and 1,3,5-N-tris(3-triethoxysilylpropyl) isocyanurate;

a silane compound that includes an amino group, such as N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and γ-anilinopropyltrimethoxysilane; a silane compound that includes an epoxy group, such as 2-(3,4-epoxy cyclohexyl)ethyltrimethoxy silane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane; a silane coupling agent that includes an acid anhydride structure, such as 2-trimethoxysilylethylsuccinic anhydride, 3-trimethoxysilylpropylsuccinic anhydride, and 3-triethoxysilylpropylsuccinic anhydride; bis(triethoxysilylpropyl) tetrasulfide; octadecyldimethyl[3-(trimethoxysilyl)propyl]ammonium chloride; and the like.

These silane coupling agents may be used either alone or in combination.

It is preferable to use a silane compound that includes an isocyanurate group or a silane coupling agent that includes an acid anhydride structure, and more preferably both a silane compound that includes an isocyanurate group and a silane coupling agent that includes an acid anhydride structure, since a cured product that exhibits excellent heat resistance and excellent transparency, and exhibits improved adhesion can be obtained.

When using both a silane compound that includes an isocyanurate group and a silane coupling agent that includes an acid anhydride structure, the silane compound that includes an isocyanurate group and the silane coupling agent that includes an acid anhydride structure are used in a mass ratio of 10:0.5 to 10:10.

The silane coupling agent is preferably used so that the mass ratio of the curable polysilsesquioxane compound according to one embodiment of the invention to the silane coupling agent (curable polysilsesquioxane compound:silane coupling agent) is 100:0.3 to 100:30, and more preferably 100:10 to 100:20.

When the silane coupling agent is used in a ratio within the above range, it is possible to obtain a curable composition that can produce a cured product that exhibits improved transparency, improved adhesion, and excellent heat resistance, and rarely shows deterioration in adhesion even when subjected to a high temperature.

The curable composition according to one embodiment of the invention may further include an additional component as long as the object of the invention is not impaired. Examples of the additional component include an antioxidant, a UV absorber, a light stabilizer, a diluent, and the like. The additional component is normally used in a ratio of 10 mass % or less based on the curable composition.

The antioxidant is added to the curable composition in order to prevent deterioration due to oxidation during heating. Examples of the antioxidant include a phosphorus-based antioxidant, a phenol-based antioxidant, a sulfur-based antioxidant, and the like.

Examples of the phosphorus-based antioxidant include phosphites, oxaphosphaphenanthrene oxides, and the like.

Examples of the phenol-based antioxidant include monophenols, bisphenols, polyphenols, and the like.

Examples of the sulfur-based antioxidant include dilauryl 3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3,3′-thiodipropionate, and the like.

These antioxidants may be used either alone or in combination. The antioxidant is normally used in a ratio of 10 mass % or less based on the curable composition.

The UV absorber is added to the curable composition in order to improve the light resistance of the resulting cured product.

Examples of the UV absorber include salicylic acids, benzophenones, benzotriazoles, hindered amines, and the like.

These UV absorbers may be used either alone or in combination.

The UV absorber is normally used in a ratio of 10 mass % or less based on the curable composition.

The light stabilizer is added to the curable composition in order to improve the light resistance of the resulting cured product.

Examples of the light stabilizer include hindered amines such as poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidine)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidine)imino}], and the like.

These light stabilizers may be used either alone or in combination.

The light stabilizer is normally used in a ratio of 10 mass % or less based on the curable composition.

The diluent is added to the curable composition in order to adjust the viscosity of the curable composition.

Examples of the diluent include glycerol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol glycidyl ether, cyclohexanedimethanol diglycidyl ether, an alkylene diglycidyl ether, polyglycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, 4-vinylcyclohexene monoxide, vinylcyclohexene dioxide, methylated vinylcyclohexene dioxide, diglycidylaniline, and the like.

These diluents may be used either alone or in combination.

The curable composition according to one embodiment of the invention may be obtained by mixing the curable polysilsesquioxane compound according to one embodiment of the invention, the silane coupling agent, and an optional additional component in a given ratio, and defoaming the mixture using a known method, for example.

The curable composition according to one embodiment of the invention thus obtained can produce a cured product that exhibits high adhesion even when exposed to high-energy light, or subjected to a high temperature.

Therefore, the curable composition according to one embodiment of the invention may suitably be used as a raw material for producing an optical part or a formed article, an adhesive, a coating material, and the like. Since the curable composition according to one embodiment of the invention can prevent deterioration in an optical device-securing material due to an increase in brightness of an optical device, the curable composition according to one embodiment of the invention may suitably be used as an optical device-securing material composition.

4) Cured Product

A cured product according to one embodiment of the invention is obtained by heating the curable composition according to one embodiment of the invention.

The heating temperature is normally 100 to 250° C., and preferably 150 to 200° C., and the heating time is normally 10 minutes to 15 hours, and preferably 30 minutes to 8 hours.

The cured product according to one embodiment of the invention exhibits high adhesion even when exposed to high-energy light, or subjected to a high temperature.

Since the cured product according to one embodiment of the invention can prevent deterioration in an optical device-securing material due to an increase in brightness of an optical device, the cured product according to one embodiment of the invention may suitably be used as an optical device-securing material. For example, the cured product according to one embodiment of the invention may suitably be used as a raw material for producing an optical part or a formed article, an adhesive, a coating material, and the like.

A cured product obtained by curing the curable composition according to one embodiment of the invention exhibits high adhesion when the adhesion is measured as described below, for example.

Specifically, the curable composition is applied to a mirror-finished surface of a silicon chip. The surface of the silicon chip to which the curable composition has been applied is placed on an adherend, and compression-bonded to the adherend, and the curable composition is cured by heating. After allowing the resulting product to stand for 30 seconds on a measurement stage of a bond tester that has been heated to a given temperature (e.g., 23 or 100° C.), adhesion between the specimen and the adherend is measured while applying stress to the bonding surface in the horizontal direction (shear direction) at a height of 50 m above the adherend.

It is preferable that the cured product have an adhesion at 23° C. of 90 N/2 mm² or more, and have an adhesion at 100° C. of 60 N/2 mm² or more.

A cured product obtained by curing the curable composition according to one embodiment of the invention exhibits excellent delamination resistance when the delamination resistance is measured as described below, for example.

Specifically, the curable composition is applied to an LED lead frame, and a sapphire chip is compression-bonded thereto. After curing the curable composition by heating at 170° C. for 2 hours, a sealing material is poured into the cup, and heated at 150° C. for 1 hour to obtain a cured product specimen. The specimen is allowed to stand at a temperature of 85° C. and a relative humidity of 85% RH for 168 hours, subjected to an IR reflow process (preheating temperature: 160° C., maximum temperature: 260° C., heating time: 1 minute), and subjected to a thermal cycle test (300 cycles, wherein one cycle consists of allowing the specimen to stand at −40° C. for 30 minutes, and allowing the specimen to stand at +100° C. for 30 minutes) using a thermal cycle tester. The sealing material is then removed to determine whether or not the device is removed (delaminated) together with the sealing material. The delamination probability is normally 25% or less when the cured product according to one embodiment of the invention is used.

5) Method for Using as Optical Device-Securing Material

A method for using as an optical device-securing material according to one embodiment of the invention includes using the curable polysilsesquioxane compound according to one embodiment of the invention or the curable composition according to one embodiment of the invention as an optical device-securing material.

Examples of the optical device-securing material include an optical device adhesive, a optical device sealing material, and the like.

Examples of the optical device include a light-emitting device such as an LED and a semiconductor laser (LD), a light-receiving device, a hybrid optical device, an optical integrated circuit, and the like.

Optical Device Adhesive

The curable polysilsesquioxane compound according to one embodiment of the invention or the curable composition according to one embodiment of the invention may suitably be used as an optical device adhesive.

When using the curable polysilsesquioxane compound according to one embodiment of the invention or the curable composition according to one embodiment of the invention as an optical device adhesive, the composition is applied to the bonding target surface of either or both of the adherends (e.g., optical device and substrate), the adherends are compression-bonded, and the composition is cured by heating to firmly bond the adherends, for example.

Examples of a material for forming the substrate to which the optical device is bonded, include glasses such as soda lime glass and heat-resistant hard glass; a ceramic; a metals such as iron, copper, aluminum, gold, silver, platinum, chromium, titanium, an alloy thereof, and stainless steel (e.g., SUS302, SUS304, SUS304L, and SUS309); a synthetic resin such as polyethylene terephthalate, polybuthylene terephthalate, polyethylene naphthalate, an ethylene-vinyl acetate copolymer, polystyrene, a polycarbonate, polymethylpentene, a polysulfone, polyether ether ketone, polyethersulfone, polyphenylene sulfide, polyetherimide, a polyimide, a polyamide, an acrylic resin, a norbomene resin, a cycloolefin resin, and a glass epoxy resin; and the like.

The heating temperature is determined taking account of the type of the curable polysilsesquioxane compound or the curable composition, and the like, but is normally 100 to 250° C., and preferably 150 to 200° C. The heating time is normally 10 minutes to 15 hours, and preferably 30 minutes to 8 hours.

Optical Device Sealing Material

The curable polysilsesquioxane compound according to one embodiment of the invention or the curable composition according to one embodiment of the invention may suitably be used as an optical device sealing material.

When using the curable polysilsesquioxane compound according to one embodiment of the invention or the curable composition according to one embodiment of the invention as an optical device sealing material, the composition is formed (molded) into the desired shape to obtain a formed article in which an optical device is enclosed, and the formed article is cured by heating to produce a sealed optical device, for example.

The curable polysilsesquioxane compound according to one embodiment of the invention or the curable composition according to one embodiment of the invention may be formed into the desired shape using an arbitrary method. A known molding method such as a transfer molding method or a casting method may be used.

The heating temperature is determined taking account of the type of the curable polysilsesquioxane compound or the curable composition, and the like, but is normally 100 to 250° C., and preferably 150 to 200° C. The heating time is normally 10 minutes to 15 hours, and preferably 30 minutes to 8 hours.

Since the sealed optical device is produced using the curable polysilsesquioxane compound according to one embodiment of the invention or the curable composition according to one embodiment of the invention, the sealed optical device exhibits excellent adhesion.

EXAMPLES

The invention is further described below by way of examples and comparative examples. Note that the invention is not limited to the following examples.

²⁹Si-NMR measurement conditions

Device: AV-500 manufactured by Bruker BioSpin K.K.

²⁹Si-NMR resonant frequency: 99.352 MHz

Probe: 5 mm (diameter) solution probe

Measurement temperature: room temperature (25° C.)

Sample rotational speed: 20 kHz

Measurement method: inverse gated decoupling method

²⁹Si flip angle: 90°

²⁹Si 90° pulse width: 8.0 μs

Repetition time: 5 s

Integration count: 9,200

Observation width: 30 kHz

Preparation of ²⁹Si-NMR sample

Fe(acac)₃ was added as a relaxation reagent in order to reduce the relaxation time.

Polysilsesquioxane concentration: 15%

Fe(acac)₃ concentration: 0.6%

Measurement solvent: CDCl₃

Internal standard: TMS

Waveform Analysis

The chemical shift of each peak of the spectrum subjected to a Fourier transform was calculated from the position of the peak top, and integrated.

Example 1

A 300 ml recovery flask was charged with 40.87 g (170 mmol) of phenyltriethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 6.52 g (30 mmol) of 2-cyanoethyltriethoxysilane (manufactured by AZmax Co.). After the addition of an aqueous solution (10.85 g) prepared by dissolving 0.05 g (0.25 mol % based on the total amount of the silane compounds) of 35% hydrochloric acid in 10.8 ml of distilled water with stirring, the mixture was stirred at 30° C. for 2 hours, and then stirred at 70° C. for 5 hours. After the addition of 100 g of propyl acetate, 0.06 g (0.5 mol % based on the total amount of the silane compounds) of 28% aqueous ammonia was added to the mixture with stirring, and the resulting mixture was stirred at 70° C. for 3 hours. Purified water was added to the reaction mixture to effect separation, and the organic layer was collected. The organic layer was washed with purified water until the aqueous layer had a pH of 7, and concentrated using an evaporator. The resulting concentrate was dried under vacuum to obtain 33.4 g of a curable polysilsesquioxane compound (A1). The curable polysilsesquioxane compound (A1) had an Mw of 1,870 and a PDI of 1.42.

The curable polysilsesquioxane compound (A1) was subjected to ²⁹Si-NMR spectrum measurement. Table 1 shows the ratio of the integral values of the peaks T1, T2, and T3.

FIG. 1 illustrates the ²⁹Si-NMR spectrum chart. In FIG. 1, the horizontal axis indicates the chemical shift (ppm), and the vertical axis indicates the peak intensity.

Comparative Example 1

A 300 ml recovery flask was charged with 40.87 g (170 mmol) of phenyltriethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 6.52 g (30 mmol) of 2-cyanoethyltriethoxysilane (manufactured by AZmax Co.). After the addition of an aqueous solution (11.72 g) prepared by dissolving 0.92 g (10 mol % based on the total amount of the silane compounds) of formic acid in 10.8 ml of distilled water with stirring, the mixture was reacted at 30° C. for 2 hours, and then held at 70° C. for 5 hours. After completion of the reaction, 100 g of ethyl acetate was added to the reaction mixture to effect separation, and the organic layer was washed with purified water until the aqueous layer had a pH of 4. The organic layer was concentrated using an evaporator, and the resulting concentrate was dried under vacuum to obtain 30.3 g of a curable polysilsesquioxane compound (A2). The curable polysilsesquioxane compound (A2) had an Mw of 1,610 and a PDI of 1.460.

The curable polysilsesquioxane compound (A2) was subjected to ²⁹Si-NMR spectrum measurement. Table 1 shows the ratio of the integral values of the peaks T1, T2, and T3.

FIG. 2 illustrates the ²⁹Si-NMR spectrum chart. In FIG. 2, the horizontal axis indicates the chemical shift (ppm), and the vertical axis indicates the peak intensity.

Comparative Example 2

33.7 g of a curable polysilsesquioxane compound (A3) was obtained in the same manner as in Example 1, except that 28% aqueous ammonia was not added. The curable polysilsesquioxane compound (A3) had an Mw of 920 and a PDI of 1.1.

The curable polysilsesquioxane compound (A3) was subjected to ²⁹Si-NMR spectrum measurement. Table 1 shows the ratio of the integral values of the peaks T1, T2, and T3.

Example 2

10 parts (parts by mass (hereinafter the same)) of 1,3,5-N-tris[3-(trimethoxysilyl)propyl] isocyanurate (“(B1)” in Table 1) (silane coupling agent) and 1 part of 3-trimethoxysilylpropylsuccinic anhydride (“(B2)” in Table 1) (silane coupling agent) were added to 100 parts of the curable polysilsesquioxane compound (A1) obtained in Example 1. After the addition of diethylene glycol monoethyl acetate to adjust the solid content to 80%, the mixture was sufficiently mixed and defoamed to obtain a curable composition 1 of Example 2.

Examples 3 and 4 and Comparative Examples 3 to 8

Curable compositions 2 and 3 of Examples 3 and 4 and curable compositions 1r to 6r of Comparative Examples 3 to 8 were obtained in the same manner as in Example 2, except that the type of the curable polysilsesquioxane compound and the amount (parts) of the silane coupling agent were changed as shown in Table 1.

Cured products of the curable compositions 1 to 3 obtained in Examples 2 to 4 and the curable compositions 1r to 6r obtained in Comparative Examples 3 to 8 were subjected to the following adhesion test, crack resistance test, and delamination resistance test, and the crack rate and the delamination rate were calculated.

Adhesion Test

The curable composition (curable compositions 1 to 3 and 1r to 6r) was applied to the mirror-finished surface of a silicon chip (2×2 mm) to a thickness of about 2 μm. The surface of the silicon chip to which the curable composition had been applied was placed on an adherend (silver-plated copper sheet), and compression-bonded to the adherend. The curable composition was cured by heating at 170° C. for 2 hours to prepare a specimen-bonded adherend. After allowing the specimen-bonded adherend to stand for 30 seconds on a measurement stage of a bond tester (“Series 4000” manufactured by Dage Co., Ltd.) that had been heated to a given temperature (23° C. or 100° C.), adhesion (N/mm²) (at 23° C. and 100° C.) between the specimen and the adherend was measured while applying stress (speed: 200 μm/s) to the bonding surface in the horizontal direction (shear direction) at a height of 50 m above the adherend. The measurement results are shown in Table 1.

Crack Resistance Test

The curable composition (curable compositions 1 to 3 and 1r to 6r) was diluted with diethylene glycol monobutyl ether acetate to adjust the solid content to 80 mass %. The curable composition was applied to the mirror-finished surface of a silicon chip (2×2 mm) to a thickness of about 2 m. The surface of the silicon chip to which the curable composition had been applied was placed on an adherend (silver-plated copper sheet), and compression-bonded to the adherend. The curable composition was cured by heating at 170° C. for 2 hours to prepare a specimen-bonded adherend. The width of a resin (fillet) protruding from the silicon chip was measured using a digital microscope (“VHX-1000” manufactured by Keyence Corporation). Fifteen specimen-bonded adherends in which a fillet had a width of 80 to 120 nm and was formed along each side of the silicon chip were selected as evaluation samples.

The fillet of each evaluation sample was observed using an electron microscope (manufactured by Keyence Corporation) to determine the number of samples in which cracks had occurred. A case where the crack rate was 0% or more and less than 25% was evaluated as “A”, a case where the crack rate was 25% or more and less than 50% was evaluated as “B”, and a case where the crack rate was 50 to 100% was evaluated as “C”.

Delamination Resistance Test

The curable composition (curable compositions 1 to 3 and 1r to 6r) was applied to an LED lead frame (“5050 D/G PKG LEAD FRAME” manufactured by Enomoto Co., Ltd.) to a diameter of about 0.4 mm, and a sapphire chip (0.5×0.5 mm) was compression-bonded thereto. After curing the curable composition by heating at 170° C. for 2 hours, a sealing material (“EG6301” manufactured by Shin-Etsu Chemical Co., Ltd.) was poured into the cup, and heated at 150° C. for 1 hour to obtain a specimen.

The specimen was allowed to stand at a temperature of 85° C. and a relative humidity of 85% RH for 168 hours, and subjected to an IR reflow process (preheating temperature: 160° C., maximum temperature: 260° C., heating time: 1 minute) (reflow oven: “WL-15-20DNX” manufactured by Sagami-Rikou Co. Ltd.). The specimen was then subjected to a thermal cycle test (300 cycles, wherein one cycle consists of allowing the specimen to stand at −40° C. for 30 minutes, and allowing the specimen to stand at +100° C. for 30 minutes) using a thermal cycle tester. The sealing material was then removed to determine whether or not the device was removed (delaminated) together with the sealing material. Each curable composition was subjected to this test 12 times.

The number of times in which the device was removed (delaminated) together with the sealing material was counted. A case where the delamination rate was 25% or less was evaluated as “A”, a case where the delamination rate was more than 25% and 50% or less was evaluated as “B”, and a case where the delamination rate was more than 50% was evaluated as “C”. It was determined that the delamination resistance was excellent when the evaluation result was “A” or “B”.

TABLE 1 Silane coupling agent Curable compound (parts) (100 parts) (B1) (B2) T1 T2 T3 Mw PDI Example 2 (A1) 10 1 0 33.4 66.6 1,870 1.42 Example 3 3 Example 4 5 Comparative Example 3 (A2) 10 1 12.73 50.77 36.5 920 1.1 Comparative Example 4 3 Comparative Example 5 5 Comparative Example 6 (A3) 10 1 13.73 53.59 32.68 1,400 1.4 Comparative Example 7 3 Comparative Example 8 5 Adhesion Curable (N/2 mm²) Crack resistance Delamination composition 23° C. 100° C. test resistance test Example 2 1 98.34 65.34 A A Example 3 2 100.26 68.95 A A Example 4 3 105.97 72.29 A A Comparative Example 3 1r 62.47 42.69 A C Comparative Example 4 2r 66.55 46.27 A C Comparative Example 5 3r 69.31 47.91 A C Comparative Example 6 4r 65.34 40.37 A C Comparative Example 7 5r 68.98 45.69 A C Comparative Example 8 6r 70.15 44.77 A C

As shown in Table 1, the cured products of the curable compositions 1 to 3 obtained using the curable polysilsesquioxane compound (A1) of Example 1 had an adhesion at 23° C. of 98 N/2 mm² or more (i.e., exhibited excellent adhesion). The cured products had an adhesion at 100° C. of 65 N/2 mm² or more (i.e., exhibited excellent heat resistance). No cracks were observed when the cured products were subjected to the crack resistance test (i.e., the evaluation result was “A”). The evaluation result was also “A” when the cured products were subjected to the delamination resistance test (i.e., the cured products exhibited excellent delamination resistance).

On the other hand, the cured products of the curable compositions 1r to 6r of Comparative Examples 3 to 8 obtained using the curable polysilsesquioxane compound (A2) or (A3) of Comparative Example 1 or 2 had inferior adhesion and inferior delamination resistance. 

The invention claimed is:
 1. A curable polysilsesquioxane compound comprising at least one structural unit represented by CHR¹X⁰-D-SiO_(3/2), wherein R¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, X⁰ is a cyano group, or a group represented by OG (wherein G is a protecting group for a hydroxyl group), and D is a single bond, or a substituted or unsubstituted divalent organic group having 1 to 20 carbon atoms, the curable polysilsesquioxane compound having a ²⁹Si nuclear magnetic resonance spectrum that has a first peak top within a range of −73 ppm or more and less than −65 ppm, has a second peak top within a range of −82 ppm or more and less than −73 ppm, and substantially does not have a peak within a range of −65 ppm or more and less than −55 ppm.
 2. The curable polysilsesquioxane compound according to claim 1, further comprising at least one structural unit represented by R²SiO_(3/2), wherein R² is an alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.
 3. The curable polysilsesquioxane compound according to claim 1, the curable polysilsesquioxane compound having the ²⁹Si nuclear magnetic resonance spectrum in which a ratio of an integral value (P2) of a peak within the range of −82 ppm or more and less than −73 ppm to an integral value (P1) of a peak within the range of −73 ppm or more and less than −65 ppm is 60 to 90%.
 4. The curable polysilsesquioxane compound according to claim 1, the curable polysilsesquioxane compound being a compound having a mass average molecular weight of 800 to 5,000.
 5. A method for producing the curable polysilsesquioxane compound according to claim 1, the method comprising a step (I) that subjects at least one compound represented by a formula (1) to polycondensation in the presence of a polycondensation catalyst, CHR¹X⁰-D-Si(OR³)₃  (1) wherein R¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, X⁰ is a cyano group, or a group represented by OG (wherein G is a protecting group for a hydroxyl group), D is a single bond, or a substituted or unsubstituted divalent organic group having 1 to 20 carbon atoms, and R³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, provided that a plurality of R³ are either identical to or different from each other.
 6. A method for producing the curable polysilsesquioxane compound according to claim 2, the method comprising a step (I) that subjects a mixture that comprises at least one compound represented by a formula (1) and at least one compound represented by a formula (2) to polycondensation in the presence of a polycondensation catalyst, CHR¹X⁰-D-Si(OR³)₃  (1) wherein R¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, X⁰ is a cyano group, or a group represented by OG (wherein G is a protecting group for a hydroxyl group), D is a single bond, or a substituted or unsubstituted divalent organic group having 1 to 20 carbon atoms, and R³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, provided that a plurality of R³ are either identical to or different from each other, R²Si(OR⁴)₃  (2) wherein R² is an alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group, and R⁴ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, provided that a plurality of R⁴ are either identical to or different from each other.
 7. A curable composition comprising the curable polysilsesquioxane compound according to claim 1, and a silane coupling agent.
 8. An optical device-securing material comprising: the curable polysilsesquioxane compound according to claim
 1. 9. An optical device-securing material comprising: the curable composition according to claim
 7. 10. The curable polysilsesquioxane compound according to claim 1, the divalent organic group is divalent hydrocarbon group.
 11. A curable polysilsesquioxane compound comprising at least one structural unit represented by CHR¹X⁰-D-SiO_(3/2), wherein R¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, X⁰ is a cyano group, or a group represented by OG (wherein G is a protecting group for a hydroxyl group), and D is a single bond, or a substituted or unsubstituted divalent organic group having 1 to 20 carbon atoms, the curable polysilsesquioxane compound having a ²⁹Si nuclear magnetic resonance spectrum that has a first peak top within a range of −73 ppm or more and less than −65 ppm, has a second peak top within a range of −82 ppm or more and less than −73 ppm, and a peak is not observed within the range of −65 ppm or more and less than −55 ppm, or, a ratio of the integral value of the peak within the range of −65 ppm or more and less than −55 ppm to the integral value of the peak within the range of −73 ppm or more and less than −65 ppm is less than 0.5% in the ²⁹Si nuclear magnetic resonance spectrum.
 12. The curable polysilsesquioxane compound according to claim 11, further comprising at least one structural unit represented by R²SiO_(3/2), wherein R² is an alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.
 13. The curable polysilsesquioxane compound according to claim 11, the curable polysilsesquioxane compound having the ²⁹Si nuclear magnetic resonance spectrum in which a ratio of an integral value (P2) of a peak within the range of −82 ppm or more and less than −73 ppm to an integral value (P1) of a peak within the range of −73 ppm or more and less than −65 ppm is 60 to 90%.
 14. The curable polysilsesquioxane compound according to claim 11, the curable polysilsesquioxane compound being a compound having a mass average molecular weight of 800 to 5,000.
 15. A method for producing the curable polysilsesquioxane compound according to claim 11, the method comprising a step (I) that subjects at least one compound represented by a formula (1) to polycondensation in the presence of a polycondensation catalyst, CHR¹X⁰-D-Si(OR³)₃  (1) wherein R¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, X⁰ is a cyano group, or a group represented by OG, wherein G is a protecting group for a hydroxyl group, D is a single bond, or a substituted or unsubstituted divalent organic group having 1 to 20 carbon atoms, and R³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, provided that a plurality of R³ are either identical to or different from each other.
 16. A method for producing the curable polysilsesquioxane compound according to claim 12, the method comprising a step (I) that subjects a mixture that comprises at least one compound represented by a formula (1) and at least one compound represented by a formula (2) to polycondensation in the presence of a polycondensation catalyst, CHR¹X⁰-D-Si(OR³)₃  (1) wherein R¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, X⁰ is a cyano group, or a group represented by OG (wherein G is a protecting group for a hydroxyl group), D is a single bond, or a substituted or unsubstituted divalent organic group having 1 to 20 carbon atoms, and R³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, provided that a plurality of R³ are either identical to or different from each other, R²Si(OR⁴)₃  (2) wherein R² is an alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group, and R⁴ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, provided that a plurality of R⁴ are either identical to or different from each other.
 17. A curable composition comprising the curable polysilsesquioxane compound according to claim 11, and a silane coupling agent.
 18. An optical device-securing material comprising: the curable polysilsesquioxane compound according to claim
 11. 19. An optical device-securing material comprising: the curable composition according to claim
 17. 20. The curable polysilsesquioxane compound according to claim 11, the divalent organic group is divalent hydrocarbon group. 